Preparation of monoethers of glycols



Patented July 31, 1934 I I A 1,968,032

UNITEDYJSTATES "PATENT @FFICE 1,968,032: 7 PREPARATION OF MONOETHERS 0F GLYCOLS' r v I Karl R. Edlund, Berkeley, Caliii, assignor to shell Development Company, San Francisco, Calif., a corporation of Delaware I No Drawing. Application October is, 1931,

Serial No. 568,650 I Claims. (Cl 260- '151) 'I'his'invention relates to the utilization of tertiary-base olefines .(olefines which are capable of yielding tertiary alcohols upon hydration) and more specifically is concerned with the preparation of glycols containing a carbon atom attached to three other carbon atoms, said carbon atom being also attached to an oxygen atom which islinked to an alkyl, aryl, or aralkyl groupingzw' r l I have found that olefines of the type 011K CHB\ I OH;

/C=CH1, c=o 1-cm c=cm CH: (11 s 7 wherein R represents an alkyl, aryl or aralkyl grouping as methyl, ethyl, propyl, --isopropy1,

'butyl, isobutyl,..amyl, phenyl, benzyl or the-like,

and wherein the bonds on the carbon atoms are satisfied .with a monovalent.substituent'such as hydrogen, alkyl groups "or the like." Thus the compound o'Hi may be regarded as a 2 -monoether of isobutylene glycol which has had a methyl grouping substi- Ltuted forahydrogen atoni' in the l-position'.

. The process comprises treating the olefine oxide, corresponding to the tertiary-base olefine,

wi th' an alcohol;preferably" one that issubst antially anhydrous, in the presence of a suitable catalyst, such as .a strongly ionizable acid of the order of H2804, HNOs, Ha'PO4 or the like.

The olefine oxide can be prepared by reacting the .tertiaryabase 'o'lefin'e with anacid of the type Its other properties are much HHalO wherein Hal represents chlorine, bromine or iodine, whereby the'halogenohydrin is first formed as an intermediate product. The oxide istthen prepared therefrom by treating the .halogenohydrin with relatively concentrated NaOH .or KOH at an elevated temperature-'- about 100 C. Thesexmethods are well knownin the art. By way of example only, reference will be ha to the production of the monoethers of isobutylene glycol, although it is to be understood that the process is capable of being carried out with other members of the class described.

.- I r V 24'gms. of isobutylene oxide and 40 gms. of anhydrous methyl alcoholwere reacted in the presence of a slight amount of 10% H2SO4 (2 drops). In order to assure more complete reaction, additional heating under a reflux condenser was necessary; Upon fractionation, a product was obtained of a boiling point of'142 C. at765 mmlanda density of It possessed the formula,v

CH: C C- a l It is miscible with water, considerable heat being evolved. The viscosity is much less than that of the glycol. It may be distilled at ordinary pressure without decomposition if substantially no acid is present.

i 'Isobutylene glycol'2-monoethyl ether was prepared in a manner similar to that for the 2- 5 methyl ether, by reacting 25' parts by volume of V isobutylene oxide with35 parts by volume of substantially anhydrous ethyl alcohol in the presence of l drop of 10% Hzso the reaction being much less vigorous. It possessed the formula .OHS

-C-OH2OH CH3 '-c.n, It has a boiling point of 147.8" C. and a density of the same as; those of the 2-methylether; 7

A considerable excess of the alcohol may advantageously be employed to secure a more complete utilization of the olefine oxide, and to minimize the formation of undesired by-products. The ether is separated from the unconsumed reagents by fractional distillation, preferably after the neutralization of the acid catalyst.

While I have in the foregoing described in some detail the preferred embodiment of my invention and some variants thereof, it will be understood that this is only for the purpose of making the invention more clear and that the invention is not to be regarded as limited to the details of operation described, nor is it dependent upon the soundness or accuracy of the theories which I have advanced as to the reasons for the results attained. On the other hand, the invention is to be regarded as limited only by the terms of the accompanying claims, in which it is my intention to claim all novelty inherent therein as broadly as is possible in view of the prior art.

I claim as my invention: 7,

'1. The process for producing monoethers of tertiary-base olefine glycols, comprising: Reacting an iso-olefine oxide, containing more than three carbon atoms to the molecule, with an alcohol and recovering therefrom acompound of the type 4. The process for producing monoethers of tertiary-base olefine glycols, comprising: Reacting a compound of the type wherein :1: represents H or CH3 with an alcohol and recovering therefrom a compound of the type C-CH-OE ZCH: OR

wherein R represents an alkyl, aryl or aralkyl group and Z represents H or CH3.

5. The new compound possessing the formula:

. CC-OH wherein R represents an aryl, alkyl or aralkyl group, :1: represents hydrogen or a hydrocarbon group and Y represents a hydrocarbon group which may be substituted.

6. The new compound possessing the formula:

CH3 Zl CCHOH I z-cH, O-R

wherein R represents an alkyl, aryl, or aralkyl group and. Z represents H or CH3.

7. The new compound possessing the formula:

CH3 I 0-011-011 l Z-CHa zn+1 wherein Z represents H or CH3 and n represents an integer or 1.

8. The new compound possessing the formula:

C--CH3OH CH3 (5R wherein R represents an alkyl, aryl or-aralkyl group. 0

group and Z represents H or CH3, at least one Z representing CH3 but not both Z simultaneously representing CH3. l

11. The new compound possessing the formula:

C K Z I C-- JHOH ZC 2 O CnHm-n wherein Z represents H or CH3, at least one Z representing CH3 but not both Z simultaneously representing CH3 and n represents an integer or 1.

12. The process for producing monoethers of tertiary-base olefine glycols, comprising: reacting an iso-olefine oxide, containing more than three carbon atoms to the molecule, with an lalcohol and recovering therefrom a compound 2120 of the type I X-C OR X wherein R represents an kyl, aryl or aralky1130 group and}; presents hydrogen or an alkyl group. I V v r 13. The new compound possessing the formula:

x X x I X A i- X-o 1 0R x x wherein R represents an aryl, alkyl, or aralkyl group, and X represents hydrogen or an alkyl group. V

14. The new compound possessingthe formula:

CH3\ Z V o-tHoH I Y z-cm 0R wherein Rrepresents' anralkyl, aryl or aralkyl 15G group and Z represents hydrogen or an alkyl wherein R represents an alkyl, aryl or aralkyl group and Z represents hydrogen or an alkyl group, at least one Z representing an alkyl group but not both Zs simultaneously representing an alkyl group.

KARL R. EDLUND. 

